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Informe 1 Inorganica Werner S Theory
Informe 1 Inorganica Werner S Theory
Abstract
The experiments by Werner on cobalt coordination compounds are a important to
understand the coordination chemistry. This report explain the observable properties of
two of the complexes of chloramine cobalt synthesized in the laboratory. The
experimental procedure demonstrate the basic postulates of Werner, that coordination
compounds can be formed because the central atoms carry the capacity to form
secondary or coordinate bonds, in addition to the normal or valence bonds.
Introduction
Alfred Werner was awarded by noble prize in 1913 for its theory about coordination
compounds. Werner's theory explains about the formation of coordinate complex
compounds, bonding of coordinate complex compounds, stability of coordinate complex
compounds and isomerism of coordinate complex compounds. A coordination compound
is a complex compound which contains a metal bonded to ligands [1]. Werner perform a
series of experiments on cobalt (III) chloride and ammonia. After the addition of silver
nitrate solution he observed that some of the chloride ions precipitated as silver chloride.
Also, he observed that the amount of silver chloride formed was related to the number of
ammonia molecules bound to the cobalt (III) chloride. For example, when silver nitrate
was added to CoCl3·6NH3, all the three chloride ions were converted to silver chloride.
However, when silver nitrate was added to CoCl3·5NH3, only two mole of silver
chloride was formed. When CoCl3·4NH3 was treated with silver nitrate, one mole of
silver chloride was formed [2]. Based on his observations, Werner postulated the
following theory: the central atom in a coordination compound exhibits two types of
valences (primary and secondary); every metal tend to satisfy both valences: every metal
has fixed number of secondary valence; and the secondary valence is always directed
toward fixed position in space [3].
Experimental Procedure
Synthesis of Ammonium Chloride
In a beaker was put 2,5 mL of NH4OH and 1,6 mL of HCl. When the reaction is
performed, the beaker was inserted in a water/ice bath for about 15 minutes, stirred by
using a magnetic bar on a stirring plate. After a complete dissolution, the beaker was
closed with a parafilm “M” paper. Around 5 minutes, there was a precipitate, and after de
15 minutes was necessary to continue to stirring for 8 minutes more. The beaker was heat
at 90°C until to reach the vaporization of the water formed and another option was put the
beaker in the oven of the laboratory for around 30 minutes, and save it in a sealed plastic
container to avoid the sample acquire impurities.
Synthesis of Compound A
In a beaker was put 1g of CoCl2*6H2O, and 0,2 g of NH4Cl, synthesized previously in the
laboratory, with 3 mL of boiling distilled water, and stirred for a better mixture with the
help of a hot plate with stir. While the solution was stirring, was added 0,04g of activated
charcoal, and the beaker was put in an ice bath until to get 10°C or less of the mixture.
Once the temperature is reached, was added 3 mL of concentrated ammonia and 40 drops
of hydrogen peroxide until to watch a yellowish-brown color while the stirring is
maintained. It was stirred for 5 minutes increasing the temperature until 50 – 60°C and it
was filter through vacuum filtration, and was added 5mL of 2% hot HCl. To the second
filtrate, was added 5 mL of cold concentrated hydrochloric acid in the flask and placed it
on ice for a few minutes. Finally, the precipitate formed was filter on vacuum and washed
with 5 mL of ethanol.
Synthesis of Compound B
In a beaker was put 0,2g of NH4Cl with 2 mL of concentrated ammonia and 1 g
CoCl2*6H2O and stirred until dissolved. Also, was added 40 drops of 30% hydrogen
peroxide and 3 mL of concentrated hydrochloric acid while the stirring was maintained.
The beaker was heat in a heat water bath for 10 minutes, was cooled and filtered when
the precipitate is complete formed. The precipitate was washed with 3 mL of distillated
cold water, following by 3 mL of ethanol and 3 mL of acetone. Finally, the obtained
precipitate was dried in the oven of the laboratory.
Density 0.791 g/mL 0.789 g/ml 0.9982 g/ml 1.20 g/mL 0.682 g/ml
Density 1.924 g/ml 1.5 g/ml 1.8 -2.1 g/ml 1.2 g/ml
*Data shown in tables was obtained from Material Safety Data Sheets by Science Lab [Web]
Toxicities of the substances used.
Hydrochloric acid (HCl) is highly corrosive, it has to be used with caution and performed
in a fume hood with the protective glass door pulled down.
Ammonium chloride (NH4Cl) is an irritant, contact with skin, eyes and clothing has to be
avoided.
Ammonia (NH3) and hydrogen peroxide 30% (H2O2) are corrosives, cause severe burns
to eyes, skin and respiratory tract.
Ethanol and Acetone are highly flammable liquids and may cause skin and eye irritation,
it has to be handled with caution.
Cobalt chloride hexahydrate (CoCl2·6H2O) is hazardous in case of skin/eye contact, of
ingestion, of inhalation.
Experimental Data
To achieve the oxidation of Cobalt (II) to Cobalt (III) others reactions must be carried
out. First, concentrated ammonia is added in order to obtain the formation of hexamine
complex ion of cobalt (II) through a ligand exchange reaction.
Finally the oxidation from Co2+ to Co3+ could be accomplished through the addition of
hydrogen peroxide H2O2.
At this point, two possible coordination complexes were synthesized. The overall
reactions are very similar:
We can explain these observations through the crystal field theory. For octahedral
complexes are 2 possible arrangements: high spin/ weak field and low spin/strong field
respectively. The energy gap is dependent on the position of the coordinate ligands in the
spectrochemical series.
- Hexamminecobalt (III) chloride ligand is NH3 which gives a low spin complex
(Big ∆o) so it will absorb small wavelengths corresponding to violet – blue color
and therefore it will emit orange color. See Figure 2.
- Chloropentamminecobalt (III) chloride has present in its coordination sphere the
Cl- ligand which will absorb high wavelengths such as yellow-orange, so it will
emit a light purple color. See Figure 2.
Conclusions
- Though Werner made made amazing arguments in explaining the geometry and bonding of
coordination compounds, he was unable to explain their color. A full explanation of how
transition metal complexes come to be so colorful had to wait for the development of
quantum mechanics and the description of energy levels in a molecule in terms of molecular
orbital theory.
- From the different measurements of spectroscopy it is possible to know if the products
obtained are the ones that were really wanted.
- Due to cobalt (III) has a high affinity for ligands where nitrogen is able to share a
pair of electrons, NH3 is added in the synthesis of these types of complexes and hydrogen
peroxide is used in order to oxidize the cobalt (II) to cobalt (III).
Final questions and requirements
3. What technique would you use to know if Cl atoms are found as chloro
(in the sphere of coordination) or as chlorides (outside the sphere of
coordination)?
By measuring electrical conductivity.
4. What is the role of the activated charcoal in the chemical reactions in which it is
used?
The activated charcoal acts as catalyst in the ligand exchange between the NH 3 and Co.
Other reaction in which activated charcoal participates as catalyst is in the oxidation
reaction that is carried out by concentrated H2O2 to convert the metal from the +2 to the
+3 oxidation state. Also it has been demonstrated that the activated charcoal gives high
yield and pure products. [4]
Bibliography
[1] Chemistry LibreTexts. (2017). 24.1: Werner’s Theory of Coordination Compounds.
[online] Available at:
https://chem.libretexts.org/Textbook_Maps/General_Chemistry_Textbook_Maps/Map%3
A_General_Chemistry_(Petrucci_et_al.)/24%3A_Complex_Ions_and_Coordination_Co
mpounds/Theory_of_Coordination_Compounds [Accessed 29 Sep. 2017].
[2] Salts, W. (2017). Werner's theory and complex salts. [online]
Chemistry.stackexchange.com. Available at:
https://chemistry.stackexchange.com/questions/7602/werners-theory-and-complex-salts
[Accessed 28 Sep. 2017].
[3] Askiitians.com. (2017). Werners Theory of Coordination Compounds - Study
Material for IIT JEE |askIITians. [online] Available at: http://www.askiitians.com/iit-jee-
co-ordination-compounds/werners-theory-of-coordination-compounds/ [Accessed 25
Sep. 2017].
[4] Anon, (n.d.). Expt. 4. Synthesis of Hexamminecobalt(III) Chloride. [online] Available
at: http://oliver.chemistry.ucsc.edu/151L/Expt4.pdf [Accessed 25 Sep. 2017].